High molecular weight products of ethylene



Patented June 18, 1946 PATENT orrlca HIGH MOLECULAR WEIGHT PRODUCTS OF ETHYLENE William Edward Richard Roland,

E. I. du Pont de Nemours a corporation of Delaware Application January 1, 1943,

mington, Dei.,

No Drawing.

Haniord, Baston, Pa, and John Wilmingt n, DeL, aeslgnors to A; Company, Wil- Sel'lal No. 471,028 8 Claims- (CL 260-4881 This invention relates to new types or products, called telomers, from ethylene and more particularly to telomers oi ethylene with oxygenated organic compounds and to the process, telomerization, for their preparation.

A number oi polymers of ethylene are known, such as, for example, those described in U. 8. Patent 2,158,553 and in U. 8. applications 383,546, 383,553, 383,554, 383,555, and 383,556, all filed March 15, 1941. These are solid products with typically polymeric properties, such as ability to be formed into films and fibers. Other polymers of ethyleneare oils, for example those polymers produced by acidic and metal halide catalysts. The oily polymers find use only in lubrication and related fields and the solid polymers have use in the plastic arts. For many applications, however, none of these polymers have the desired properties. Thus the solid ethylene polymers, even those of low molecular weight, are relatively insoluble, have poor solvent retention, and are incompatible with parafiin and other natural waxes. Furthermore, the low molecular weight polymers of this type are soft solids and the higher molecular weight products are tough, stringy, and coherent. In contrast the new ethylene telomers of this invention have a different chemical composition and show good solubility characteristics. They are aifin and waxes over wide ranges of composition; they have high retention of solvents, especially wax solvents; they are extremely hard and form a continuous hard film without stringing or sticking, especially when laid down from a gelled composition containing solvent.

An object of this invention is to produce new products from ethylene. Another object is to produce telomers of ethylene, more specifically telomers of ethylene and oxygenated organic compounds. Yet another object is to provide a process for the preparation of telomers from ethylene and more particularly telomers from ethylene with oxygenated organic compounds. Other objects and advantages of the invention will appear hereinafter.

The novelty of the products of this invention and of the reaction by which they are formed is such that for a clear understanding a new set oi terms has been coined. The reaction has been called telomerization (from the Greek telos, meaning "end plus the Greek mer, meaning "part"). Telomerization is defined as the process of reacting, under polymerization conditions, a molecule YZ, which is called a telogen, with more than one unit of a polymerizable compound compatible with par-,

having ethylenic unsaturation, called a taxogen, to farm products called telomers, having a new carbon to carbon bond and the formula SUN .2, wherein (Ala is a divalent radical formed from a. plurality o! taxogen molecules, the unit A being called "taxomon," n being any integer greater than 1 and Y and Z being fragments of the telogen attached terminally to the chain 01' taxomons. some telomerization reactions have 10 been described in copending application Ser. No.

Telomerization is not to be confused with interpolymerization. It is known, for example, that, under conditions similar to those described above, ethylene can be interpolymerized with a wide variety of unsaturated compounds. In such interpolymerizations a plurality of molecules of each reactant, the ethylene and the unsaturated compound, enter into the formation of every polymer chain, and the resulting product is a high molecular weight polymeric material containing recurring units of each species or reactants. In telomerization reactions, however, substantially one molecule 01' the telogen enters into reaction with the growing polymer chain, and the average molecular weight of the product is very much lower than that of an interpolymer or polymer formed under similar conditions. In most instances, telomerization leads to products comprised essentially of telomers of the above structure. However, depending upon the nature of the telogen and the reaction conditions, the products produced by the process of this invention sometimes appear to contain, on the average, less than one molecule of the telogen per polymer chain, but none contain more than one molecule of chemically combined telogen per molecule oi the telomer. One explanation for this, which should not be construed as limiting the invention in any manner, is that the telomerization reaction is accompanied in some cases by a small amount of a side reaction which yields a relatively low molecular weight material, free of combined addenda oi the telogen.

The objects of this invention have been accomplished by the discovery that ethylene can be telomerized with a saturated organic compound containing only carbon, hydrogen, and oxygen in the presence of a suitable telomerization catalyst. Generally speaking, the telomerization conditions include elevated temperatures, for example, from about 50 to 300 0., and the use 01', preferably, a peroxygen-type catalyst. Telomerization catalysts arethose which have ll been shown to yield free radicals and to be cataongeninthemesenoeof this invention range from a e to hard waxes and all may be formed by heating ethylene and a saturated organic comcarbon, hydrogen, and a peroxygen-type catalyst Imder superatmospheric pressure. The saturated organic and used as telogcn may be means for heating and agitating the reaction mixture. Preferably, means are also provided for deoxygenating ethylene and, for continuous operation, suitable pumps and metering devices for controlling rates of addition or various reactants. The reaction may be operated as a batch process, a semi-continuous process or a continuous process. The following discussion illustrates of the reaction.

A prBsureesistant reaction vessel is charged with a peroxide catalyst and the desired telogen. If desired the telogen may be diluted with an inert solvent, preferably a saturated hydrocara less active telogen.

pounds which telogens and demonstrate suitable conditions for operation All parts are by weight unless otherwise stated 4 cured with ethylene and heating and agitation are started. a reaction time of 15.25 hours, throughout cooled, bled of excess ethylene. opened and the reaction mixture discharged. This reaction mixture consists of a soft, pasty composition of unreacted diethyl malonate and The diethyl malonate is extracted several times the waxy solid filtered parts of an ethylene was which melts at 113-1 14 C. and has an intrinsic viscosity of 0.16 (as measured on a solution in xylene at (3.). On analysis this wax is found to contain 81.45% carbon and 12.81% hydrogen from which lated that the product has a mole ratio of ethylene/diethyl malonate-all/l. ethylene/malonic ester telomer yields an acid with a neutral equivalent 01' 1521.

Example 2.A silver-lined high pressure reaction vessel is with parts of ethyl acetoacetate and 0.4 part of benzoyl peroxide. The vessel is closed, placed in a shaker machine. pressured with ethylene and heating and agitationare started. g a reaction time of 12 hours throughout which the temperature is maintained at 94-95 0. he pressure at 7659'75 atmospheres, there is a total observed pressure drop of atmospheres. The vessel is cooled. bled of excess ethylene, opened and the reaction wax has an ethylene/ethyl acetoacetate mole ratio of 35: 1.

Example 3.A stainless steel-lined high pressure reaction vessel is charged with 100 parts of secondary butyl acetate and 0.2 part of benzoyl peroxide. The vessel is closed. evacuated to remove residual air, placed in a 810-1000 atmospheres, there is a total observed pressure drop of 445 atmospheres. is cooled, bled of excess ethylene, opened and the reaction mixture discharged. The ethylene/secondary butyl acetate wax is separated from unwhich melts at Ill-113 trinsic viscosity of 0.1 (as measured on a 5 5% solution in xylene at 85" 0.). 0n melting the wax becomes a mobile liquid which sets up on cooling to a hard, This telomer, when substituted for carnauba wax, gave a paste polish which easily rubbed to an extremely hard glossy finish.

Example 4.-A stainless steel-lined high pressure react on vessel is charged with 100 parts of methyl propionate and 0.2 part of benzoyl per- The vessel is closed. evacuated to remove residual air. placed in a shaker machine and Heating and agitation contents discharged.

I co'sity of 0.12 (as measuredon a great advantage of this wax ening 000atmoepheres.thereisatotelpreeauredropoi'lttatmospheres. Thevesselis cooled. bled of excess ethylene. openedand the yields 80 parts oi ethylene/methyl propionate wax which melts at 118-120" C.. has an intrinsic vis- 56% solution in xylene at 85' C.) and has a saponiiication number 01 11.8. This wax, when substituted for carnaubawaxin apastepolishiormulaisioundto polish readily to a high, hard. glossy finish. The over other synthetic waxes hitherto described is its remarkable hardeilect on paraiiin. its compatibility over wide ranges with parailln and its high retention oi wax solvents.

Emmple 5.A stainless steel-lined high pressure reaction vessel is charged with 100 parts oi methyl methoxyacetate and 0.2 part oi benaoyl peroxide. The vessel is closed. evacuated to remove residual air, placed in a shaker machine and heating'and agitation started. During a reaction time oi 17.2 hours throughout which the temperature is maintained at 75-80 C. and the pressure at 650-055 atmospheres. there is a total observed pressure drop oi 425 atmospheres. The vessel is cooled. bled of excess ethylene, opened and the contents discharged. This reaction mixture yields 24 parts or an ethylene/methyl methoxyacetate wax which melts at 110 C., after soitening at 70 C. and has an intrinsic viscosity oi 0.07 (as measured on a solution in xylene at 85 0.). The saponiflcation number of this wax is found to be 39.0. From this it may be calculated that the wax has an ethylene/methyl methoxyacetate hole ratio of 47/ 1.

Example 6.-A stainless steel-lined high pressure reaction vessel is charged with 100 parts of methyl n-butyrate and 0.2 part of benzoyl peroxide. The vessel is closed. evacuated to remove residual air, placed in a shaker machine, pressured with ethylene and heating and agitation are started. During a reaction time oi 16.7 hours throughout which the temperature was maintained at ll-100 C. and the pressure at 500-050 atmospheres. there is a total observed pressure drop of 620 atmospheres. The vessel is cooled. bled oi excess ethylene. opened and the contents discharged. This reaction mixture yields 36 parts of ethylene/methyl n-butyrate wax which melts at 118-120 C., has an intrinsic viscosity of 0.28 (as measured on a solution at 85 C.) and a saponiilcation number of 14.9. The molecular weights calculated from the viscosity and from the saponiilcation number are 3060 and 3700 respectively. From these data, based on physical and chemical properties respectively, it is evident that telomerization is the chief reaction.

Example 7.-A stainless steel-lined high pressure reaction vessel is charged with 100 parts of ethyl orthoiormate and 0.2 part oi benzoyl peroxide. The vessel is closed, evacuated to remove residual air, placed in a shaker machine. pressured with ethylene and heating and agitation started. During a reaction time of 17.4 hours,

throughout which the temperature is maintained at 78-86 C. and the pressure at 770-050 atmospheres, there is a total observed pressure drop of 295 atmospheres. The vessel is cooled, bled oi excess ethylene. opened and the contents discharged. This reaction mixture yields 18 parts of ethylene/ethyl orthoiormate wax which has an intrinsic viscosity of 0.32 (as measured on a solution in xylene at 85 C.) and which melts at 115-120 C. to a syrupy liqui On cooling. the meltsetsuptoahardglossysolid.

Example 8.-A stainless steel-lined high Dressure reaction vessel is charged with 100 parts of dimethyl adipate and 0.2 part oi benaoyl peroxide. The vessel is closed. evacuated to remove residual air, placed in a shaker machine. pressured with ethylene, and heating and agitation started. During a reaction time oi 16.25 hours, throughout which the temperature is maintained at 73-87 C. and the pressure at 550-950 atmospheres. there is a total observed pressure drop oi 255 atmospheres. The vessel is cooled. bled oi excess ethylene. opened and the contents diacharged. This reaction mixture yields 10 parts of ethylene/dimethyl adipate wax which has an intrinsic viscosityoi 0.15 (as measured on a 6% solution in xylene at C.) and which melts at 115 C. to a tree flowing liquid. On cooling. the melted wax sets up with a smooth. glossy. hard finish.

Example 9.A stainless steel-lined high pressure reaction vessel is charged with parts of methyl acetate, 0.5 part of hexachloroethane and 0.5 part of sodium tetraborate. The vessel is closed, evacuated to remove residual air. placed in a shaker machine and heating and agitation started. During a reaction time 01 15.25 hours, throughout which the temperature is maintained at 250-258" C. and the pressure at 505-055 atmospheres. there is a total observed pressure drop of 1170 atmospheres. The vessel is cooled, bled oi excess ethylene, opened and the contents discharged. This reaction mixture yields 92 parts oi a soit, slightly tacky. coherent wax resembling beeswax in its gross properties. This wax has an intrinsic viscosity of 0.16 (as measured on a solution at 85 0.), melts at 80 C. and has a saponiflcation number of 14.1. The molecular weight calculated from viscosity is 2800, that calculated irom the saponiiication number, is 3800. These data, based on physical and chemical properties respectively, show that telornerization oi the methyl acetate accounts for substantially all of the reaction.

Example 10.--A stainless steel-lined high pressure reaction vessel is charged with 100 parts of lA-dioxane and 0.2 part of benzoyl peroxide. The vessel is closed, evacuated to remove residual air, placed in a shaker machine, pressured with ethylene and heating and agitation are started. During a reaction time 01' 16.25 hours throughout which the temperature is maintained at 75-81" C. (except for momentary surges to C. and 94 C.) and the pressure at 650-950 atmospheres. there is a total observed pressure drop oi 485 atmospheres. The vessel is cooled, bled oi excess ethylene, opened and the contents discharged. This reaction mixture yields 27 parts oi a hard wax which melts to a syrupy fluid at C. The wax has an intrinsic viscosity of 0.25 (as measured on a solution in xylene at 85 C.) and contains 84.27% carbon and 13.72% hydrogen. From this analysis it may be calculated that the wax has an ethylene/1,4-dioxane mole ratio oi 54:1.

Example 11.--A stainless steel-lined hi h pressure reaction vessel is charged with 100 parts of tetrahydroiurane and 0.2 port oi benzoy] peroxide. The vessel is closed, evacuated, placed in a shaker machine and heating and agitation are started. During a reaction time oi 16.05 hours throughout which the temperature was maintained at 60 to 102 C. and the pressure at 750 to 1000 atmospheres. there is a total observed pressure drop of 855 atmospheres. The vessel is cooled, bled of excess ethylene. opened and the contents discharged. Thi reaction mixture yields 44 parts of ethylene/tetrahydroi'urane wax which melts at 115 C. The melt is a clear, limpid fluid 1nd sets up on cooling to a. smooth, hard, lossy solid. Thh: wax has an intrinsic viscosity of 0.19 (as measured on a 55% solution of xylene at 85 C.)

Example 12.-A stainless steel-lined high pressure reaction vessel is charged with 100 parts of 1,3-dioxolane. The remaining space of the reaction vessel is filled with air in which there is 0.05% of oxygen. as calculated on the amount of ethylene introduced. The vessel is closed. placed in a shaker machine, pressured with ethylene and heating and agitation are started. During a reaction time oi 9 hours throughout which the temperature is maintained at 172-176 0. (except for one brief surge to 198 C.) and the pressure at 855-915 atmospheres, there is a total observed pressure drop of 480 atmospheres. The vessel is coole bled of excess ethylene. opened and the contents discharged. This reaction mixture yields 42.5 parts oi ethylene/1,3-dioxolane wax which melts at C. after prior softening at 45 C. This wax is a stiff grease rather like lanolin though somewhat stifler and more coherent. The wax contains 81.65% carbon and 13.71% hydrogen from which it may be calculated that the mole ratio of ethylene to dioxolane is 22:1. This corresponds to a molecular weight of 690 which is in good agreement with'the observed molecular weight of 775 as determined ebulloscopically. This two of wax is admirably suited for use as a drawing lubricant in the drawing of metals and may also be used as a lanolin substitute in cosmetics and pharmaceuticals.

Example 13.-A stainless steel-lined high pressure reaction vessel is charged with 100 parts oi 1,3-dioxolane and 0.2 part of hydrazine sulfate. The vessel is closed. evacuated to remove residual air, placed in a shaker machine. pressured with ethylene andheating and agitation are started. During a reaction time of 15.5 hours. throughout which the temperature is maintained at 223-238 C. and the pressure at 840-930 atmospheres, there is a total observed pressure drop 01 130 atmospheres. The vessel is cooled, bled or excess ethylene, opened and the contents discharged. This reaction mixture Yields 42 parts or soft wax which melts at 90 C. after prior softening oi 40-45 C. This wax is found (ebulloscopically) to have a molecular weight of 625. This wax closely resembles that illustrated in Example 12.

Example 14.A stainless steel-lined high pressure reaction vessel is charged with 100 parts of ethylal and 0.3 part by volume of diethyl peroxide. The vessel is closed, evacuated, placed in a shaker machine, pressured with ethylene and heating and agitation are started. During a reaction time of 16.75 hours, throughout which temperature is maintained at l30-145 C. and the pressure at 500-950 atmospheres, there is a total observed pressure drop of 605 atmospheres. The vessel is cooled, bled of excess ethylene, opened and the contents discharged. This reaction mixture yields 52 parts of wax which melts at 100-102 C. The intrinsic viscosity of this wax is 0.15 (as measured on a solution in xylene at 85 (2.). This wax contains 1.72% ethoxyl which corresponds to a molecular weight of about 5000.

Example 15.-A stainless steel-lined high pressure reaction vessel is charged with 100 parts 01 8 1,3-dioxolane which has been blown with air until the peroxide content (as measured by liberclosed, evacuated to remove residual air, placed in a shaker machine. pressured with ethylene, and heating and agitation are started. During a reaction time 01' 17.5 hours throughout which the temperature is maintained at 79-82 C. and the pressure at 005-910 atmospheres, there is a total observed pressure drop of 215 atmospheres. The vessel is cooled. bled or excess ethylene, opened and the contents discharged. This reaction mixture yields 26 parts of ethylene/1,3-dioxolane wax which melts at 113-115 C. and has an intrinsic viscosity of 0.09 (as measured on a /&% solution in xylene at C.). Proximate analysis Of the wax shows the wax to contain 83.41% carbon and 14.22% hydrogen from which it may be calculated that the product has an ethylene/dioxolane mole ratio of 46: 1.

Example 16.A stainles steel-lined high pressure vessel is charged with parts 01 1,3-dioxolane, 0.5 part of sodium persuli'ate and one part of sodium tetraborate. The vessel is closed, evacuated to remove residual air. placed in a shaker machine, pressured with ethylene. and heating and agitation are started. During a reaction time of 17.25 hours throughout which the temperature is maintained at 79-81 C. and the pressure at 860-950 atmospheres, there is a total observed pressure drop of 225 atmospheres. The vessel is cooled, bled of excess ethylene, opened and the contents discharged. This reaction mixture yields 8 parts of ethylene/dioxolane wax which melts at 116 to 117 C.

Example 17.A silver-lined high pressure reaction vessel is charged with 100 parts of acetone and 0.5 part of benzoyl peroxide. The vessel is closed. evacuated to remove residual air, placed in a shaker machine, pressured with ethylene, and heating and agitation are started. During a reaction time of 10 hours throughout which the temperature is maintained at 97-101 C. and the pressure at 665-900 atmospheres, there is a total observed pressure drop of 50 atmospheres. The vessel is cooled, bled oi excess ethylene, opened, and the contents discharged. The reaction mixture yields 18 parts of ethylene/acetone wax which has an intrinsic viscosity of 0.03 (as measured on a 0.125% solution in xylene at 85 C.). melts at 113 C., and is found to have a molecular weight 01' 1350. Proximate analysis shows the product to have an ethylene/acetone mole ratio of 33:1.

Example 18.A silver-lined high pressure reaction vessel is charged with 50 parts 01 cyclohexanone, 0.5 part hexachloroethane, and 2.0 parts 01 borax. The vessel is closed, evacuated. placed in a shaker machine, pressured with ethylene and heating and agitation are started. During a reaction time of 10 hours, throughout which the temperature is maintained at 249-256 C. and pressure at 400-505 atmospheres, there is a total observed pressure drop at 655 atmospheres. The vessel is cooled, bled of excess ethylene. opened and the contents discharged. This reaction mixture is dissolved in benzene, i'lltered and steam distilled. The polymer is separated from the residual water by filtration and dried. There is thus obtained 14 parts 01' ethylene/cyclohexanone telomer which melts at 80 C. and has a molecular weight of 272.

Example 1.9.-A silver-lined high pressure reaction vessel is charged with 100 parts oi propicnic acid, 0.5 part of hcxachloroethane and 0.5 port sodium tetraborate. The vessel is closed. evacuated, placed in a shaker machine, pressured with ethylene and heating and agitation are started. During a reaction time or 5.5 hours, throughout which the temperature is maintained at ass-253 C. and pressure at 845-950 atmospheres, there is a total observed pressure drop or 445 atmospheres. The vessel is cooled, bled oi excess ethylene, opened and the contents discharged. This reaction mixture yields 62 parts oi soi't acid wax 64.8, corresponding to a molecular weight of 886.

Example 20.A ilver-lined high pressure reaction vessel is charged with 80 parts or propionic anhydride, 0.5 part of hexachloroethane and 0.5 part of sodium tetraborate. The vessel is closed, evacuated to remove residual air, placed in a shaker machine, pressured with ethylene, and heating and agitation are started. During a reaction time or 12.5 hours, throughout which the temperature is maintained at 107-212 C.. and the pressure at 050-950 atmospheres, there is a total observed pressure drop of 860 atmospheres. The vessel is cooled, bled or excess ethylene, opened, and the contents discharged. The whole reaction mixture is diluted with water and filtered. The solid precipitate is saponiiied by heating in pyridine solution with methanolic potassium hydroxide. The hydrolysate is then poured into a large volume oi water and iiltered. The filtrate, which shows a high degree surface activity, is evaporated to remove pyridine and methanol and then taken up in water. This aqueous solution ioams strongly, wets sulfur instantiy and shows detergent action on soiled cotton fabric. The water insoluble matter left from the saponiilcation is a tough coherent wax resembling beeswax in its gross physical properties.

Example 21. A stainless steel-lined high pressure reaction vessel is charged with 900 parts at methanol and 0.2 part benaoyl peroxide. The vessel is closed, placed in a shaker machine, pressured with ethylene and heating and agitation are started. During a reaction time of 16.75 hours, throughout which the temperature is maintainedat 79-81 0., pressure at 855-900 atmospheres, there is a total observed pressure drop 01 660 atmospheres. The vessel is cooled, bled of excess ethylene, opened, and the contents discharged. This reaction mixture yields 16 parts or hard ethylene/methanol wax which has an intrinsic viscosity of 0.28 (as measured on a solution in xylene at 85 C.) and which melts at 115-111 C. The melted wax is slightly viscous but sets up on cooling to a hard glossy solid.

Example 22.A stainless steel-lined high pressure reaction vessel is charged with 100 parts of absolute ethanol and 0.2 part oi. benzoyl peroxide. The vessel is closed, evacuated to remove residual air, placed in a shaker machine, pressured with ethylene and heating and agitation are started. During a reaction time oi, 17.5 hours, throughout which the temperature is maintained at 70-100 C. and the pressure at 690-955 atmospheres, there is a total observed pressure drop or 835 atmospheres. The vessel is cooled, bled oi excess ethylene, opened, and the contents discharged. This reaction mixture yields 43 parts of ethylene/ethanol wax which has an intrinsic viscosity oi 0.88 (as measured on a $55 solution in niche at 05' C.) and which melts at 110-190 C. The wax meltsto a syrupy fluid and -oneoolingsetsuptoahardglossy which has an acid number or surereaction vessel is charged with 100 parts anhydrous diethyl ether and 0.2 part of benzoyl peroxide. The vessel is closed, evacuated to remove residual air, placed in a shaker machine and pressured with ethylene. Heating and agitation are started, and during a reaction time of 17 hours, throughout which the temperature is maintained at 78-82 C. and the pressure at 075-990 atmospheres, there is a total observed drop oi! 210 atmospheres. The vessel is cooled, bled or excess ethylene, opened and the contents discharged. The reaction mixture yields 9 parts or ethylene/diethylether telomer. The product melts at 116-118" 0., has an intrinsic viscosity oi 0.11 (as measured on a solution in xylene at C.) and contains 0.63% ethoxyl.

Example 24.-A stainless steel-lined reaction vessel is charged with 100 parts of vinyl acetate, 200 parts of 1,3-dioxolane and 0.4 part of benzoyl peroxide. The vessel is closed, evacuated, placed in a rocker mechanism and pressured with ethylem: to 600 atmospheres (450 grams). Heating and agitation are started and during a reaction time oi 15.5 hours, throughout which the temperature is maintained at '73-'16" C. and the pressure at 695-970 atmospheres, there is a total observed pressure drop or 730 atmospheres. The vessel is cooled, bled of excess ethylene, opened and the contents discharged. This reaction mixture yields 20? parts of ethylene/vinyl acetate] 1,3-dioxolane telomer which melts at C., has an intrinsic viscosity oi 0.20 (as measured on a solution in Xylene at 85 C.) and a saponiflcation number of 55.4. The viscosity is equivalent to a molecular weight oi 3590 and from this and the saponiflcation number the telomer composition is calculated to be ethylene: vinyl acetate: l,3-dioxolane=1l5:3.5:l. This is a tou wax which can be polished to a high gloss.

It has been stated that products oi. this invention are telomers of ethylene with saturated organic compounds containing only carbon, hydrogen and oxygen and that they are believed to have the structure H(C2H4)1\R, wherein H is abstracted from the telogen and R is the residue of said telogen. Whether this suggested structure is correct in all details is not entirely certain but as is adequately shown by the examples, the products contain chemically bound fragments of thetelogen and the functional groups 0! these fragments can be determined by standard analytical methods. In this respect particularly and in physical properties generally, the new telomers of this invention diiler irom more low molecular weight polymersoi ethylene. Nevertheless, whatever the mechanism by which such telomers are formed or whatever their structure, the description of the products is adequate and the process for their preparation is sufliciently well illustrated that no limitations of theory are imposed on the invention.- defining the classes of saturated organic compounds which act as telogens. possibly gives a clearer picture of the nature of the products.

'The telogens employed as reaction media and as reactants in this invention are saturated organic compounds containing only carbon, hydrogen and oxygen. By saturated organic compounds is meant any compound which is tree of oleilnic unsaturation and is meant to exclude such polymerizable compounds as vinyl esters, acrylic esters, and other derivatives or acrylic acids. Suitable classes oi this type of telogen are saturated alcohols. ether-s, acids. esters. anhy- Inample aa-s stainless steel-linedhigh prel- II drides, aldehydes, ketones and acetals. Preferred The next paragraph in which R", R, and 11"" are free of oleflnic unsaturation, may be alike or diilerent, may be alkyl, aryl, aralhl or alkaryi, and R" and B may be hydrogen. Preferred classes of compounds coming within the scope of this formula are others. esters, anhydrides, and acetals. Acetal is used in its broadest sense and includes the subgroups of formula and of hotels. These telogens herein employed in general are relatively less reactive than other telomerizing agents, as, e. 8., the polyhalom For this reason, the molecular weight or telomers from polyhaiomethanes prepared under comparable conditions, in general, would be much lower.

Telomerization reactions, like peroxide catalyzed polymerizations, are highly sensitive to traces of impurities or inhibitors. Because 01' this and because of the wide variety of sources or these classes of compounds, it is especially desirable that the compounds be prepared or special 1y purified to rigid requirements. For example, some acetals, though boiling at the correct temperature have been found to show no reaction with ethylene, whereas the same acetal carefully purified, e. g., by redistillation from sodium or hydroquinone in a nitrogen atmosphere, will give high yields of ethylene/metal wax. Similarly, it is preferable that esters be carefully purified. One convenient method is by distilling an ester of normal purity from about 2% by weight of phosphorus pentoxide. Other types of telogens are preferably purified by appropriate methods which are well known and widely described.

Inasmuch as it is not convenient or feasible to weigh accurately the ethylene used in these reactions, the ratio of telogen to ethylene is best expressed as a ratio of weight to volume; for example, in most or the examples the amount or telogen ranges from 50 to 200 parts and, in the reactor employed the remainder of the reaction space of from 350 to 200 volumes is occupied by ethylene under the conditions of temperature and pressure prevailing. Ordinarily, this volume of ethylene amounts to from 100 to 200 parts by weight. Preferred limits of ratios of telogen to ethylene thus range from 1:2 to 2:1, expressed by weight, though ratios ouilide this, e. g. from 1:5 to 50:1 are operable. Wax-like products from such telogens as ethers and esters have, on a molar basis. a ratio of telogen to ethylene 01' 1 to 20, and generally from 1 to 30, although the ethylene chain may be considerably longer.

The telogen is preferably used in its purest form e. 8. 11 weight based on the telogen, do not appreciably hinder the reaction. Likewise, organic solvents may be used to dilute the telogen. For this, saturated aliphatic hydrocarbons a second polymeriaable organic compound conliquid pound may be used. Die 24.

Th telomerimtion reaction between ethylene and the above-defined telogens does not occur in the absence of a telomerlmtion catalyst. The catalysts used in the Broom 01 this invention are agents which are eflective as talysts for the polymerization of ethylene and which are, at the same time, ineflective as catalysts for the Priedel-Craits reaction. It must be understood that the process or the present inv tion is not reactions present process. While the agents used in the present reaction are cmnmoniy spoken of as catalysts, it is thought that they do not act as an inert catalyzing agentsuch, for example, as carbon black, but that they take part in the reaction in some way. In fact, it may be that a better term for these action promoters. However, since reaction promoters have been called catalysts so generall in the art, and since the of the present process are not clearly established, the term "catalyst" has been employed herein.

Both polymerization 01 vinyl compounds and model-Crafts reactions with these same type compounds are so well known that any one skilled in the art will be able, without iiliculty, toselect a catalyst which would be effective to promote polymerization and ineirective to promote Frledel- Crai'ts reaction. By way of example, the following suitable telomerization catalysts may be employed: diacyl peroxides, such as diacetyl peroxide, dipropionyl peroxide, dihutyryl peroxide, dilauroyl peroxide, acetyl clibenzoyl peroxide;

ydrazine metal carbonates. The temperatures employed in the practice of this invention may vary over a wide range. The temperature to be employed will depend to a large degree on other conditions. Temperature is most critically dependent on the nature of the catalyst, for exam le. diacyl peroxides and per-sulfates generally operate best in a range from 50 to 150 C. Oxygen, ethane and hydrazine compounds generally require considerably elevated temperatures, e. g. from to 250 C. Diethyl peroxid is intermediate and preferably operates in a temperasents would be re- 13 ture range from 100 to 200 C. The temperature chosen for carrying out this telomerization is to some extent dependent on the nature of the telegen. As shown b the examples, certain teioge'ns such as methyl propionate and 1.3-dioxolane are extremely reactive and may lead to difll'cultly controllable temperature surges during the initial stages of the reaction. In other cases the telogen is much less reactive and under the same conditions of temperature reacts sluggishly. In order to offset this the temperature is conveniently raised.

Since ettnrlene is a gas. its telomerization reactions are carried out under superatmospheric pressure. In order to attain a high yield and a high space-time yield these reactions are generally carried out at pressures above 3 atmospheres. The preferred pressure range is from about 400 to 1000 atmospheres. The latter figure should not be taken as an absolute upper limit since this is determined solely by the strength of available equipment. Operation at higher pressures is possible and for high rates of reaction highly desirable. Pressure is a variable which is dependent to some degree on the temperature; thus at high temperatures a relatively rapid rate of reaction may be attained at low pressure, while at low to intermediate temperatures more elevated pressures are necessary to attain the same rate of reaction.

As has been pointed out before, telomerization reactions are extremely sensitive to impurities. For this reason the ethylene used should be of the highest purity practical. Small amounts of methane, ethane. nitrogen, hydrogen, carbon dioxide and oxygen are tolerable. Small amounts of the first six of these have negligible effect on telomerization reactions. However, the oxygen concentration is highly critical, inasmuch as large amounts of oxygen completely inhibit peroxide catalyzed telomerization reactions at relatively low temperatures when it is present to the extent of more than 0.1% by weight. In order to reduce the oxygen concentration of ethylene to below this figure commercial ethylene is deoXY- genated, for example, by passage over hot copper or by scrubbing with a strong reducing agent. Oxygen can, however, act as a catalyst as shown above, if its concentration is quite small. e, g. below 0.1% and preferably below 0.075%. The activity of oxygen as a catalyst is only apparent at relatively elevated temperatures, for example, above 150 C. and preferably from 150 to 250 C.

In the practice of this invention all equipment which comes in actual contact with the polymerization system is preferably fabricated of or lined with materials which do not rapidly catalyze the decomposition of peroxide to molecular oxygen. Suitable examples of such materials are stainless steels, silver, lead, tin, aluminum, enamel and glass.

A continuous process oiIers obvious advantages. especially for commerctal or semi-technical scales of operation. Among the chief of these is the ease of control of reaction conditions for these highly exothermic reactions. In telomerization by a continuous process the time of contact may be readily controlled and thus the rats of removal of the heat oi. reaction and temperature are easily controlled. The high space-time yield of continuous operation again ferred for large scale operation.

for telomeriaation'of ethylene described in this invention may take :l'or'examplathemixtureofethylenaperoxidc catalyst and telogen may be pumped through a tubular reactor, a portion of which is heated to the desired temperature. The ethylene may be bubbled through a solution of the catalyst in the desired telogen with continuous removal of the product and simultaneous replacement of fresh telogen solution of catalyst or the ethylene and telogen may be pumped separately, mixed, and then passed through a reaction acne. Alternatively, the mixture of ethylene and telogen can be pumped through a system into which, at various intervals. is injected a solution of the catalyst.

For the best results in the practice of this invention it is generally desirable to agitate the reactants. This is meant to include any means for obtaining intimate contact of all reactants such as by vigorous shaking of the whole reaction system, stirring as in an autoclave type reactor, or by eiilcient bubbling of the gaseous phase of the system through the liquid phase or by turbulent how of a gas-liquid system.

The telomers comprising this invention have found large numbers of uses. The most important are those hard waxy telomers like ethylene/methyl propionate and ethylene/ether waxes which have been found to be extremely romising substitutes for carnauba and other natural waxes. Thus, these have been found excellent for use in paste polishes. emulsion polishes. in which the carnauba wax of the polish formula is replaced by the telomer. These have been found to be excellent for preparations of automobile polish. floor paste polish, for shoe polishes, for emulsion floor polishes. These have also been found to have lubricating action and to be of use for drawing metals. as a bullet lubricant, and as a modifier for lubricating oils. Most of the waxes comprising this invention are extremely hard. Many are found to be as hard or harder than the best grades of carnauba wax. This makes the material a desirable substitute for use as a hardening agent for wax candles. Similarly, they have found use for molding Dictaphone records and as wax in carbon paper inks. Waterrepeilent properties of natural wax are duplicated in these new telomers and they are thus found useful in moisture-proofing paper and fabrics. These have been used for paper coating and impregnation, for textile finishes, for moistureprooflng paper and textiles, for coating paper by the melt method. Other uses are as a paper size, as a fiatting agent for finishes. as an anthfloodins agent for enamels.

We claim:

1. A process which comprises heating an allphatic ester of an aliphatic carboxylic acid free from oleilnic unsaturation and which contains at least one hydrogen on the alpha carbon atom and a. peroiwgen-type catalyst at a temperature between 50 and 250 C. under ethylene pressure above 200 atmospheres.

2. A process for the preparation of a saturated aliphatic hydrocarbon radical radical substituted organic acid ester which comprises heating, under ethylene pressure above 200 atmospheres, ethylene, an organic acid ester free or oleflnic unsaturation. and a pere rs -type cataly 3. A process for the preparation of a saturated aliphatic hydrocarbon radical substituted methyl ropionate which comprises heatins. under ethy one pressure above 200 atmospheres, ethylene, methyl propionate, and benaoyl peroxide.

4. A wax-like product obtained by the process ofclaimscontainingalinearchainofatleast 30 ethylene groups per molecule.

16 5. A process which comprises heating an alialiphatic hydrocarbon radical substituted ormie phatlc ester or an aliphatic carboxylic acid tree acid ester which comprises heating under ethylfrom oleflnlc unsaturation which contains at ene pressure above 200 atmospheres an organic least one hydrogen on the alpha carbon atom and acid ester tree of oleflnic unsaturation and e pera. peroxy catalyst at a temperature between 50 5 oxy catalyst.

and 250 C. and under ethylen pressure above 8. The wax-like product obtained by the proc- 200 atmospheres. es; of claim 7 which contains at least 40 carbon 6. The wax-like product obtained by the procatoms per molecule.

es of claim 5 which contains a linear chain of at least 20 ethylene Bro 7. A process for the preparation 01' a saturated JOHN RICHARD ROLAND.

Certificate of Correction Patent N 0. 2,402,137. June 18, 1946.

WILLIAM EDWARD HANFORD ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered atent re uiring correction as follows: Column 5, line 36, Example 5, for hole res. mole co um 14, lines 65 and 66, claim 2, and line 71, claim 3, strike out ,ethylenc,; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 3rd day of September, A. D. 1946.

LESLIE FRAZER,

First Assistant Oornms'su'omr of Patents.

ups. l0 WILLIAM EDWARD HANFORD.

16 5. A process which comprises heating an alialiphatic hydrocarbon radical substituted ormie phatlc ester or an aliphatic carboxylic acid tree acid ester which comprises heating under ethylfrom oleflnlc unsaturation which contains at ene pressure above 200 atmospheres an organic least one hydrogen on the alpha carbon atom and acid ester tree of oleflnic unsaturation and e pera. peroxy catalyst at a temperature between 50 5 oxy catalyst.

and 250 C. and under ethylen pressure above 8. The wax-like product obtained by the proc- 200 atmospheres. es; of claim 7 which contains at least 40 carbon 6. The wax-like product obtained by the procatoms per molecule.

es of claim 5 which contains a linear chain of at least 20 ethylene Bro 7. A process for the preparation 01' a saturated JOHN RICHARD ROLAND.

Certificate of Correction Patent N 0. 2,402,137. June 18, 1946.

WILLIAM EDWARD HANFORD ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered atent re uiring correction as follows: Column 5, line 36, Example 5, for hole res. mole co um 14, lines 65 and 66, claim 2, and line 71, claim 3, strike out ,ethylenc,; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 3rd day of September, A. D. 1946.

LESLIE FRAZER,

First Assistant Oornms'su'omr of Patents.

ups. l0 WILLIAM EDWARD HANFORD. 

